EP4209484B1 - Verfahren zur herstellung von elektronenarmen olefinmonomeren - Google Patents
Verfahren zur herstellung von elektronenarmen olefinmonomeren Download PDFInfo
- Publication number
- EP4209484B1 EP4209484B1 EP22184081.2A EP22184081A EP4209484B1 EP 4209484 B1 EP4209484 B1 EP 4209484B1 EP 22184081 A EP22184081 A EP 22184081A EP 4209484 B1 EP4209484 B1 EP 4209484B1
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- European Patent Office
- Prior art keywords
- acid
- catalyst
- process according
- iii
- mol
- Prior art date
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- 239000000178 monomer Substances 0.000 title claims description 96
- 230000002950 deficient Effects 0.000 title claims description 31
- 150000001336 alkenes Chemical class 0.000 title claims description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 claims description 105
- -1 methylene compound Chemical class 0.000 claims description 90
- 239000003054 catalyst Substances 0.000 claims description 87
- 230000008569 process Effects 0.000 claims description 85
- 239000002841 Lewis acid Substances 0.000 claims description 68
- 239000003426 co-catalyst Substances 0.000 claims description 67
- 150000007517 lewis acids Chemical class 0.000 claims description 63
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 62
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 56
- 239000002253 acid Substances 0.000 claims description 52
- 239000007848 Bronsted acid Substances 0.000 claims description 46
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 39
- BPGDAMSIGCZZLK-UHFFFAOYSA-N acetyloxymethyl acetate Chemical group CC(=O)OCOC(C)=O BPGDAMSIGCZZLK-UHFFFAOYSA-N 0.000 claims description 29
- 239000003381 stabilizer Substances 0.000 claims description 29
- 150000002989 phenols Chemical class 0.000 claims description 28
- 150000004053 quinones Chemical class 0.000 claims description 28
- 125000001424 substituent group Chemical group 0.000 claims description 28
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 26
- 229910001848 post-transition metal Inorganic materials 0.000 claims description 25
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 20
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 19
- 150000007513 acids Chemical class 0.000 claims description 19
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 19
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 16
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 14
- 150000002825 nitriles Chemical class 0.000 claims description 14
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 14
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 13
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 12
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229920002866 paraformaldehyde Polymers 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 9
- BAYGVMXZJBFEMB-UHFFFAOYSA-N 4-(trifluoromethyl)phenol Chemical compound OC1=CC=C(C(F)(F)F)C=C1 BAYGVMXZJBFEMB-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 7
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 7
- 150000002602 lanthanoids Chemical class 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000004682 monohydrates Chemical class 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- BGJSXRVXTHVRSN-VMIGTVKRSA-N 1,3,5-trioxane Chemical group [13CH2]1O[13CH2]O[13CH2]O1 BGJSXRVXTHVRSN-VMIGTVKRSA-N 0.000 claims description 4
- 239000004322 Butylated hydroxytoluene Substances 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 4
- 229940095259 butylated hydroxytoluene Drugs 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 235000019282 butylated hydroxyanisole Nutrition 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- RJMMFJHMVBOLGY-UHFFFAOYSA-N indium(3+) Chemical compound [In+3] RJMMFJHMVBOLGY-UHFFFAOYSA-N 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004255 Butylated hydroxyanisole Substances 0.000 claims description 2
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 2
- 229940043253 butylated hydroxyanisole Drugs 0.000 claims description 2
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 96
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 75
- 150000008063 acylals Chemical class 0.000 description 36
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 33
- 230000015572 biosynthetic process Effects 0.000 description 26
- MLIREBYILWEBDM-UHFFFAOYSA-M 2-cyanoacetate Chemical compound [O-]C(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-M 0.000 description 21
- 229920001651 Cyanoacrylate Polymers 0.000 description 19
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical class OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 19
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 18
- 239000007858 starting material Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 14
- 238000013459 approach Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 238000005755 formation reaction Methods 0.000 description 14
- 230000035484 reaction time Effects 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 12
- 229940053009 ethyl cyanoacrylate Drugs 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000004821 distillation Methods 0.000 description 11
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 10
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011968 lewis acid catalyst Substances 0.000 description 9
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000376 reactant Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 150000007975 iminium salts Chemical class 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 4
- JJJFUHOGVZWXNQ-UHFFFAOYSA-N enbucrilate Chemical compound CCCCOC(=O)C(=C)C#N JJJFUHOGVZWXNQ-UHFFFAOYSA-N 0.000 description 4
- 229950010048 enbucrilate Drugs 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
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- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 4
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 3
- DJACTCNGCHPGOI-UHFFFAOYSA-N butyl 2-cyanoacetate Chemical compound CCCCOC(=O)CC#N DJACTCNGCHPGOI-UHFFFAOYSA-N 0.000 description 3
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- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000004508 fractional distillation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- MMPZYDUOPLQDHR-UHFFFAOYSA-N hexa-1,5-diene-3,4-dione Chemical compound C=CC(=O)C(=O)C=C MMPZYDUOPLQDHR-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 239000003208 petroleum Substances 0.000 description 3
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- 238000011160 research Methods 0.000 description 3
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- 241000894007 species Species 0.000 description 3
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- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
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- SFLXUZPXEWWQNH-UHFFFAOYSA-K tetrabutylazanium;tribromide Chemical compound [Br-].[Br-].[Br-].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC SFLXUZPXEWWQNH-UHFFFAOYSA-K 0.000 description 2
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- FWLIRCFOOMVZKX-UHFFFAOYSA-N 1,1,3-trioxo-1,2-benzothiazole-2-sulfonic acid Chemical compound C1=CC=C2S(=O)(=O)N(S(=O)(=O)O)C(=O)C2=C1 FWLIRCFOOMVZKX-UHFFFAOYSA-N 0.000 description 1
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229910007607 Zn(BF4)2 Inorganic materials 0.000 description 1
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- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- NSGXIRUYPVAGGQ-UHFFFAOYSA-N acetonitrile;nitromethane Chemical compound CC#N.C[N+]([O-])=O NSGXIRUYPVAGGQ-UHFFFAOYSA-N 0.000 description 1
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- 229940037003 alum Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
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- 238000010923 batch production Methods 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
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- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- HNLZCOJXSLDGKD-UHFFFAOYSA-N dichloro(iodo)methane Chemical compound ClC(Cl)I HNLZCOJXSLDGKD-UHFFFAOYSA-N 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- APGUSRKQFBWUPZ-UHFFFAOYSA-K disulfooxyalumanyl hydrogen sulfate Chemical compound [Al+3].OS([O-])(=O)=O.OS([O-])(=O)=O.OS([O-])(=O)=O APGUSRKQFBWUPZ-UHFFFAOYSA-K 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- GLQOFBCJADYRKR-UHFFFAOYSA-K erbium(3+);trifluoromethanesulfonate Chemical compound [Er+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F GLQOFBCJADYRKR-UHFFFAOYSA-K 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- VLKXTTDBMHCVHM-UHFFFAOYSA-J hydrogen sulfate;zirconium(4+) Chemical compound [Zr+4].OS([O-])(=O)=O.OS([O-])(=O)=O.OS([O-])(=O)=O.OS([O-])(=O)=O VLKXTTDBMHCVHM-UHFFFAOYSA-J 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- MJDVPXPHTLECMC-UHFFFAOYSA-N prop-2-enoyl cyanide Chemical compound C=CC(=O)C#N MJDVPXPHTLECMC-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/19—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and carboxyl groups, other than cyano groups, bound to the same saturated acyclic carbon skeleton
Definitions
- the present invention relates to a process for preparing electron deficient olefin monomers comprising nitrile, carboxylic ester or carboxylic acid functional groups, which find application in the field of fast curing adhesives.
- Electron deficient monomers bear two electron withdrawing groups (EWGs) on the same carbon atom of their olefinic bond. These monomers are highly susceptible to polymerisation initiated by electron rich species due to polarisation of their double bond.
- Cyanoacrylate monomers (CAs) are examples, represented by general formula (I), wherein R is typically an alkyl group. Whereas various CAs are known, only ethyl cyanoacrylate, (ECA) of formula (II) is mass-produced at significant scale due to demand, since it is the major component of commercially important instant adhesives.
- ethyl cyanoacetate (NC-CH 2 -CO 2 Et) is the starting material used to produce ECA.
- This class of starting materials is considered 'active' due to the acidity of the central methylene hydrogen atoms that are easily removed by bases.
- the relative reactivity of active methylene compounds therefore depends on the conditions in which they are deployed as well as the type, strength and combinations of the geminal EWGs they possess, as explained in Sankar et al., Current Chemistry Letts., 2012, 1(3), 123-132 .
- Cyanoacetates are highly reactive under base catalysed reaction conditions.
- iminium or ammonium salts are instead used as organocatalysts, rather than reagents, for reaction between active methylene compounds and at least a stoichiometric quantity of a methylene diacetate, MeCOOCH 2 OOCMe (an acylal, i.e., a compound with a gem -dicarboxy or gem- bis(acyloxy) moiety) that acts as a methylene transfer reagent, as disclosed in US 9,670,145 .
- MeCOOCH 2 OOCMe an acylal, i.e., a compound with a gem -dicarboxy or gem- bis(acyloxy) moiety
- This method reports highest isolated monomer yields for CAs when the acylal is first prepared in a separate process.
- N-based nitrogen-based
- Protonic acids are used generally to neutralise or acidify the reaction or process environment.
- the object of the present invention is a process for preparing electron-deficient olefin monomers.
- the object of the present invention is a process for preparing electron-deficient olefin monomers, wherein an active methylene compound of general formula (III), EWG-CH 2 -Z 1 (III) wherein the two electron withdrawing groups represented by EWG and Z 1 , are selected from nitrile, carboxylic ester, and carboxylic acid functional groups, is reacted with either
- the authors of the present invention have developed a simple solution for preparing electron-deficient olefin monomers by using acid-based catalyst systems, preferably used in conjunction with promoters for Knoevenagel reactions, to convert active methylene compounds to said olefin monomers.
- the authors of the present invention have developed a process for preparing electron-deficient olefin monomers that allows the direct preparation of the monomer without the need to include a step of thermal depolymerisation of a prepolymer. It is an efficient process for preparing said monomers in stable environments from readily available starting materials under acid catalysis to circumvent the use of N-based catalysts and allow isolation of said reactive monomers directly from the reaction medium. Since all CA processes generate large quantities of by-products from the various reagents that transfer or otherwise provide saturated methylene groups, atom-efficient processes are most desirable wherein by-products may be used to regenerate key reagents for the monomer forming reaction itself. Said electron-deficient olefin compounds are reactive monomers that find application in the field of fast-curing adhesives. These include cyanoacrylates, among other compounds.
- the process of the invention allows the preparation of high purity monofunctional and polyfunctional electron-deficient olefin monomers independently of whether they are liquid or solid.
- the present invention comprises two main embodiments.
- One embodiment is referred to as a "three-component embodiment” and another, as a “two-component embodiment".
- both embodiments comprise additional minor components that form the catalyst systems and stabilisers that are described separately for clarity.
- the three-component embodiment is a preferred embodiment. So named because it comprises three groups of reactants, thus:
- the active methylene compound is a cyanoacetate
- the source formaldehyde is 1,3,5-trioxane
- the carboxylic acid anhydride is a symmetrical carboxylic acid anhydride, for example, acetic anhydride.
- the reaction of the three-component embodiment is catalysed by a catalyst system that comprises at least one acid or, at least one acid and at least one co-catalyst.
- the catalyst system allows the in-situ formation of an acylal by reaction of the source of formaldehyde and the carboxylic acid anhydride.
- the reaction between the acylal and the active methylene compound leads to the electron-deficient olefin monomer.
- the active methylene compounds of the process of the invention are the reactants that determine the type of electron-deficient olefin monomer that is produced.
- the active methylene compounds have general formula (III) EWG-CH 2 -Z 1 (III)
- the preferred electron withdrawing functional groups in the active methylene compounds of the present invention represented by EWG and Z 1 in compounds of general formula (III) are selected from the group of nitrile (-CN), carboxylic ester (-CO 2 R), and carboxylic acid (-CO 2 H), more preferably from nitrile and carboxylic ester.
- the active methylene compound comprises a nitrile and a carboxylic ester as electron withdrawing functional groups.
- Active methylene compounds of general formula (III) are widely known. Many such compounds are commercially available, for example various alkyl cyanoacetates and 1,3-dicarbonyl compounds and the literature is replete with references to the preparation of others.
- the preparation of specialized cyanoacetates that may also be multifunctional or comprise mixed functionalities, is described in, for example, US 3,092,611 , US 4,202,920 , US 4,364876 , US 4,528,357 , US 5,140,084 , US 5,175,337 , US 6,096,848 , US 6,271,410 , US 6,281,310 , US 7,262,313 , EP-A-0 459 617 , WO-A-2007/046647 , WO-A-2008/069515 , WO-A-2009/053482 , Vijayalaskhmi et al., J.
- Adhesion Sci. Tech., 1990, 4(9), 733-750 Guseva et al., Izv. Akad. Nauk., Ser. Khim., 1993,3, 523-525 , Kotzev et al., Die Makromol. Chem., 1980, 92(1421), 41-52 , Blanco et al., Bull. Soc. Chim. Belg., 1989, 98(12), 923-929 , Renner et al., J. Polym. Sci., Polym. Chem Ed., 1985, 23, 2341-2359 , Senchenya et al., Izv. Akad. Nauk.
- the active methylene compounds of general formula (III) comprise a carboxylic acid group within an ester group, for example produced by the reaction of NCCH 2 COO - Na + with bromoacetic acid.
- the active methylene compounds of general formula (III) comprise an electron withdrawing group that is the carboxylic acid group while the other electron withdrawing group is preferably selected from nitrile and carboxylic ester.
- Some of the latter compounds are commercially available, such as cyanoacetic acid. The preparation of others has been described by, for example, Levonis, et al., Aust. J. Chem., 2007, 60, 821-82 , Xia et al., J. Chem. Res., 2005, 332-334 , Kimura, M., Tetrahedron Lett., 2018, 59, 1295-1300 , Mao et al., Eur. J. Org. Chem., 2020, (5), 525-538 , or Bew et al., Chemistry, 2017, 23(19), 4557-4569 .
- one or more active methylene compound may be used in the three-component embodiment.
- the concentration of active methylene compound(s) serves as a reference to the concentration of other components expressed in either mol% or stoichiometric/molar ratio relative to the compound(s) of general formula (III).
- the preferred active methylene compound is a cyanoacetate, or a mixture of cyanoacetates, or a mixture of cyanoacetate and cyanoacetic acid. In a more preferred embodiment, the preferred active methylene compound is a cyanoacetate.
- the three-component embodiment is contingent on the formation of the acylal, which requires the presence of a source of an aldehyde and a carboxylic acid anhydride.
- the source of the aldehyde is a source of formaldehyde.
- the source of formaldehyde is selected from dry formaldehyde gas, paraformaldehyde, and 1,3,5-trioxane.
- the preferred source of formaldehyde is 1,3,5-trioxane, whether recrystallized or not, more preferably in a dry form achieved through any convenient means, such as recrystallisation from acetone, ethyl acetate, petroleum ethers, and mixtures thereof, or sublimation.
- a preferred molar concentration of 1,3,5-trioxane relative to compound of general formula (III) is 1.25:1, more preferably 1.1:1, and yet more preferably 1:1.
- the three-component embodiment in the process of the invention requires the presence of a source of formaldehyde and a carboxylic acid anhydride to obtain in situ the acylal, which, under the Knoevenagel reaction conditions, further reacts with the active methylene compound of formula (III) to obtain the electron-deficient olefin monomers.
- Q 1 and Q 2 are the same group, i.e., the carboxylic acid anhydride is symmetrical.
- the carboxylic acid anhydride is selected from acetic anhydride and propionic anhydride.
- the carboxylic acid anhydride is acetic anhydride.
- Triflic anhydride may also be used in the present invention and promotes faster reaction still than acetic anhydride. However acetic anhydride is more convenient to handle.
- carboxylic acid anhydrides may be readily prepared from carboxylic acids, for example by the mild methods described in Kim et al., Synthetic Comm., 2001, 31(3), 395-399 , and references cited therein.
- acetic acid is generated as a by-product in the process of the invention, and may thus be re-used to reproduce acetic anhydride for use again in said process by using such methods.
- the process of the invention is atom-efficient in this regard, unlike the indirect or direct methods employing paraformaldehyde or direct methods producing salts, all of which generate residue as waste.
- the carboxylic acid anhydride for the three-component embodiment is employed usually in the molar concentration range ratio 1:5, preferably in the molar concentration range ratio 1:3, more preferably in the molar concentration range ratio 1:2.5, and yet more preferably in the ratio 1:2, where the ratios refer to active methylene compound of general formula (III) to acid anhydride compound of general formula (IV), that is the ratio of (III) to (IV).
- the reaction of the three-component embodiment is catalysed by a catalyst system that comprises at least one acid or at least one acid and at least one co-catalyst selected from the group of phenolic compounds, with one or more substituents, and quinone compounds.
- the catalyst system also functions as a stabiliser system although additional polymerisation inhibitors may also be incorporated.
- An objective of the present invention is the direct preparation of electron-deficient olefinic monomers by reaction between active methylene compounds and acylals, either formed in situ or preformed, with novel efficient catalyst systems that are acid based.
- compounds such as hydroquinone used in concentrations as low as 0.05 mol% can catalyse the nucleophilic addition of active methylene compounds activated by benzoquinone at similar concentrations to substituted aldehydes in Knoevenagel reactions as indicated in, for example, Takakura et al., Org. Biomol. Chem., 2020, 18, 6594-6597 , but neither hydroquinone or benzoquinone independently catalyse acylal formation.
- acid-based catalyst systems produce electron deficient olefin monomers by facilitating reaction between acylals and active methylene compounds whether or not the components comprising the catalyst system independently catalyse either acylal formation, or, Knoevenagel reaction.
- the catalyst systems suitable to be used in the process of the invention, provide multiple means of activation of all reactants and are preferably provided through the combination of acid catalysts with co-catalysts especially when either acid catalyst or co-catalyst cannot independently influence both acylal formation and Knoevenagel reaction. Catalyst systems comprising such combinations also facilitate direct reaction between active methylene compounds and pre-formed acylals. It has been surprisingly found that effective co-catalysts for Lewis or Br ⁇ nsted acid catalysts are selected from phenolic compounds and quinone compounds.
- the catalyst systems described herein thus comprise either specific Lewis acids, combinations of Lewis acids and Br ⁇ nsted acids, combinations of Lewis acids or Br ⁇ nsted acids with aforementioned co-catalysts, or combinations of Lewis acids and Br ⁇ nsted acids and said co-catalysts.
- the catalyst system is selected from:
- the co-catalyst is selected from phenol, hydroquinone, p-methoxyphenol, p-trifluoromethyl phenol, 1,4-benzoquinone, 1,4-naphthoquinone, and mixtures thereof. More preferably, the co-catalyst is hydroquinone.
- the catalyst system catalyses a reaction between a cyanoacetate active methylene compound and methylene diacetate (an acylal), produced in situ, by acid catalysed reaction between acetic anhydride and a source of formaldehyde, preferably 1,3,5-trioxane.
- the acid catalyst system present in the process of the invention also stabilises against cyanoacrylate polymerisation.
- the catalyst system comprises a combination of Lewis acid, preferably a post-transition metal Lewis acid, a Br ⁇ nsted acid and a co-catalyst selected from phenolic compounds, with one or more substituents, quinone compounds, and mixtures thereof, preferably selected from phenol, hydroquinone, p -methoxyphenol, p -trifluoromethyl phenol, 1,4-benzoquinone, 1,4-naphthoquinone, and mixtures thereof.
- Lewis acid preferably a post-transition metal Lewis acid, a Br ⁇ nsted acid
- a co-catalyst selected from phenolic compounds, with one or more substituents, quinone compounds, and mixtures thereof, preferably selected from phenol, hydroquinone, p -methoxyphenol, p -trifluoromethyl phenol, 1,4-benzoquinone, 1,4-naphthoquinone, and mixtures thereof.
- an alkyl cyanoacetate as active methylene compound, a source of formaldehyde, preferably 1,3,5-trioxane, acetic anhydride
- the catalyst system comprises a combination of Lewis acid, preferably a post-transition metal Lewis acid, a Bronsted acid and a co-catalyst selected from phenolic compounds, with one or more substituents, quinone compounds, and mixtures thereof, preferably selected from phenol, hydroquinone, p -methoxyphenol, p -trifluoromethyl phenol, 1,4-benzoquinone, 1,4-naphthoquinone, and mixtures thereof.
- Lewis acids suitable to be used in the process of the invention are selected from transition metals halides, post-transition metal-based halides, preferably trihalides, alkali earth metal-based perchlorates, such as Mg(ClO 4 ) 2 , and Lanthanide metal based, such as Yb(OTf) 3 .
- Lewis acids are selected from the group of post-transition metals, more preferably from indium (III) trihalide and gallium (III) trihalide, preferably trichlorides, and most preferably the Lewis acid is InCl 3 .
- the Lewis acid catalyst may be used in the concentration range comprised between 0.05 mol% and 10 mol% relative to active methylene compound of general formula (III). Preferably it is used in the range comprised between 0.1 mol% and 5 mol%, and most preferably in the range comprised between 0.5 mol% and 1.5 mol%.
- concentration range comprised between 0.05 mol% and 10 mol% relative to active methylene compound of general formula (III).
- it is used in the range comprised between 0.1 mol% and 5 mol%, and most preferably in the range comprised between 0.5 mol% and 1.5 mol%.
- the use of such low catalyst loadings further adds convenience in processing, since catalysts are not required to be separated from reaction mixtures for subsequent distillations, and reactions may be conducted in continuous mode.
- Bronsted acids are suitable to be used in the process of the invention.
- they are selected from p -toluene sulfonic acid, benzene sulfonic acid, and aralkylsulfonic acids.
- the Br ⁇ nsted acid is p -toluene sulfonic acid, whether anhydrous form or as monohydrate.
- the Bronsted acid catalyst may be used in the concentration range comprised between 2.5 mol% and 15 mol%, relative to active methylene compound of general formula (III), preferably it is used in the range comprised between 4 mol% and 6 mol%.
- the co-catalysts are preferably used in the concentration range comprised between 0.01 mol% and 10 mol%, relative to active methylene compound of general formula (III), more preferably between 0.01 mol% and 6 mol%.
- Lewis acid and Bronsted acids are preferably used in concentrations comprised between 0.5 mol% and 1 mol% and between 2 mol% and 8 mol%, respectively, relative to active methylene compound of general formula (III).
- Lewis acids and co-catalysts are preferably used in concentrations comprised between 0.5 mol% and 1mol% and between 0.02 mol% and 8 mol% respectively, relative to active methylene compound of general formula (III)
- Br ⁇ nsted acid and co-catalysts are preferably used in concentrations comprised between 1 mol% and 5 mol% and between 0.02 mol% and 8 mol%, respectively, relative to active methylene compound of general formula (III)
- Lewis acids and Br ⁇ nsted acids and co-catalysts are preferably used in concentrations comprised between 0.5 mol% and 1 mol% and between 2 mol% and 8 mol% and between 0.02 mol% and 8 mol%, respectively, relative to active methylene compound of general formula (III).
- Electron-deficient olefin monomers such as CAs
- CAs are readily polymerised by electron rich species. Since they are vinyl monomers, CAs are also susceptible to polymerisation by free radicals even if this is a less preferred mechanism. Synthesis and manipulation of these reactive monomers in all process steps necessitates special attention to stabilisation in both the liquid phase and vapour phase. In turn this requires use of non-volatile and volatile stabilisers to prevent polymerisation by any mechanism.
- equipment that is in direct contact with the monomers must be passivated, for example glassware or stainless-steel components are pre-washed with strong Bronsted acids such as sulfuric acid, thoroughly rinsed with distilled water and dried.
- Liquid CA monomers isolated by distillation are usually collected onto a quantity of combined acidic and free radical stabilisers pre-determined according to the expected volume of monomer to be collected.
- additional stabilisers may optionally be employed in the reaction and distillation processes as well as in final distillates from the reaction.
- the process of the invention comprises the use of stabilisers selected from acid stabilisers and radical stabilisers.
- Volatile acid stabilisers are well known in the prior art to curtail polymerisation in the vapour trail in distillation processes with electron deficient monomers.
- Lewis or Br ⁇ nsted acids such as boron trifluoride etherate, SO 2 , trifluoracetic acid, most preferably boron trifluoride etherate, may be used in concentration ranges comprised between 0 wt% and 0.05 wt% in bulk reaction milieux and distillation pots, and comprised between 0.0005 wt% and 0.005 wt% in monomeric distillates.
- Non-volatile free radical stabilisers such as, for example, 2,2'-methylenebis-(6-tert-buthyl-p-cresol) (Stabilizer "2246"), pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate (Irganox ® 1010) may be used in concentration ranges comprised between 0.01 wt% and 3.0 wt%, preferably between 0.01 wt% and 1.5 wt%, in bulk reaction milieux and distillation pots.
- Stabilizer 2,2'-methylenebis-(6-tert-buthyl-p-cresol)
- Irganox ® 1010 pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate
- concentration ranges comprised between 0.01 wt% and 3.0 wt%
- Volatile free radical stabilisers may also be used in the process of the invention.
- Said stabilisers include, for example, hydroquinone (HQ), 4-methoxyphenol (MeHQ), butylated hydroxyanisole (BHA), and butylated hydroxytoluene (BHT), and may be used in concentration ranges comprised between 0.01 wt% and 3.0 wt%, preferably between 0.01 wt% and 1.5 wt%, in bulk reaction milieux and distillation pots, and comprised between 0.1 wt% and 0.5 wt% in monomeric distillates.
- HQ hydroquinone
- MeHQ 4-methoxyphenol
- BHA butylated hydroxyanisole
- BHT butylated hydroxytoluene
- the three-component embodiment may be conducted solventless or in the presence of solvents such as, for example, toluene, p -xylene, or 1,4-dioxane.
- Hydrocarbon solvents also provide a useful means of pre-drying reaction components, if necessary, by formation of azeotropes with any water that may be present and use of Dean-Stark equipment as well known to those skilled in the art.
- reaction mixture is diluted by 1.5 to 10-fold by volume, preferably by 2-fold by volume.
- reaction mixtures are continuously agitated by any appropriate means such as stirring and/or shearing in batch reactions, or, through use of static or dynamic mixers or spinning discs in continuous or flow reactors.
- the reactions are generally conducted in a timeframe of 1 to 10 hours depending on the reactivity of the substrates, the catalyst system and the temperature of reaction.
- preferred reaction temperatures are in the range comprised between 60°C and 140°C, for reaction time in a range comprised between 0.5 h and 10 h, preferably between 100°C and 130°C for reaction time between 1 h and 5 h, and more preferably between 115°C and 125°C for reaction time between 1 h and 2 h.
- the reactions are conducted within 2 h at 120°C employing a catalyst system comprising InCl 3 at 1 mol%, p-toluene sulfonic acid at 5 mol% and hydroquinone at 5 mol%.
- the parameters required to optimise continuous reaction depend on the type of reactor employed and are determined in ways known to those skilled in the art by tracking conversion to product through sampling as a function of time and systematic variation of reaction component flow rates and agitation speeds.
- benchtop 1 H-NMR Spinsolve 60MHz, Magritek Ltd.
- a preferred continuous reactor is the SpinPro rector (Flowid bv) because of its capability to process inhomogeneous mixtures with exceptional mixing.
- the two-component embodiment comprises two groups of reactants, thus:
- the active methylene compound is a cyanoacetate
- the methylene diester is selected from methylene diacetates, for example, methylene diacetate.
- the reaction of the two-component embodiment is catalysed by a catalyst system that comprises a Bronsted acid and at least one co-catalyst selected from the group of phenolic compounds, with one or more substituents, and quinone compounds.
- the catalyst system also functions as a stabiliser system although additional polymerisation inhibitors may also be incorporated.
- the active methylene compounds used in the three-component embodiment also apply to the two-component embodiment.
- the acylal compound is a compound with a gem -dicarboxy or gem -bis(acyloxy) moiety, such as, for example, methylene diacetate.
- an acylal is produced in situ, in the two-component embodiment, the acylal is provided after its pre-formation in an independent reaction.
- a means to activate the active methylene compound with a suitable catalyst system to facilitate its reaction with the acylal is also required.
- acylal, methylene diester, methylene diacetate, 1,1-geminal diacetate are used interchangeably to describe compounds of general formula (V): wherein Q 1 and Q 2 are independently selected from C 1 -C 4 linear and branched alkyl groups, and said terms also refer to acylals, wherein the central methylene group is substituted as shown in the general formula (VI): wherein R a selected from alkyl, aryl, and aralkyl group.
- Methylene diesters of formula (VI) that bear a substituent on the central methylene group result from reaction of carboxylic acid anhydrides with substituted aldehydes have been extensively reviewed in Sydnes et al., PINSA, 2002, 68(2), 141-174 .
- Acylals are usually prepared by the acid catalysed reaction of a carboxylic acid anhydride with an aldehyde, however they may also be prepared by transfer of a methylene group from donors such as methylene dihalides (e.g., dichloro- or diiodomethane) to carboxylates.
- donors such as methylene dihalides (e.g., dichloro- or diiodomethane) to carboxylates.
- Methylene diacetates comprising a central group that is unsubstituted (thus, -OCH 2 O-) result from reaction of carboxylic acid anhydrides with linear or cyclic sources of formaldehyde such as paraformaldehyde or 1,3,5-trioxane respectively, in the presence of acid or metal-based catalysts and are also described in, for example, US 3, 927,078 , Hoffmann et al., Catal. Sci. Technol., 2018, 8, 5594-5603 , and Tomi ⁇ ka et al., Angew. Chem. Int. Edn., 1962, 1(4), 211.
- Preferred acylals used in the two-component embodiment of the present invention exclusively comprise an unsubstituted central methylene group (-OCH 2 O-).
- the groups Q 1 and Q 2 are preferably equivalent in the acylals of choice and selected from C 1 -C 4 linear and branched alkyl groups.
- acylals such as, for example, AlCl 3 , Amberlyst, Envirocatsw, montmorillonite, zeolites, Nafion-H, Dowex ® 50WX4, Caro's acid, Wells-Dawson heteropolyacid, Mo/TiO2-ZrO 2 solid acid, P 2 O 5 /SiO 2 , P 2 O 5 /montmorillonite, FeSO 4 , FeCl 3 , AlCl 3 , TMSCI-Nal, Sc(OTf) 3 , I 2 , NBS, PCl 3 , H 2 SO 4 , Cu(OTf) 2 , LiBF 4 , H 2 NSO 3 H, BF 3 , (NH 4 ) 2 Ce(NO 3 ) 6 , LiOTf, Zn(BF 4 ) 2 , AlPW 12 O 40 , ZrCl
- Preferred catalysts for the formation of acylals are selected from those known to function under mild conditions in independent reactions, such as the alkali metal based Lewis acid LiBr described in Sampath Kumar et al., J. Chemical Research (S), 2000, 86-87 , the alkali earth based Lewis acid Mg(ClO 4 ) 2 described in Yang, in J. Chemical Research, 2006, 199-202 , Lanthanide based Lewis acids such as Yb(OTf) 3 and Er(OTf) 3 , described in Dalpozzo et al., op.
- transition metal Lewis acid catalysts such as FeCl 3 described in the review Rezayati et al., Research on Chemical Intermediates, 2020, DOI: 10.1007/s11164-020-04176-x
- post-transition metal Lewis acid catalysts such as indium and gallium trihalides described in Yin et al., Tetrahedron, 2007, 48, 3119-3122 , and Kumar et al., ARKIVOC, 2007, 27-33 .
- the catalyst system allows the reaction between the acylal and the active methylene compound leading to the electron-deficient olefin monomer.
- the catalyst system comprises a Br ⁇ nsted acid and at least one co-catalyst.
- Br ⁇ nsted acids are suitable to be used in the process of the invention.
- they are selected from p-toluene sulfonic acid, benzene sulfonic acid, and aralkylsulfonic acids.
- the Br ⁇ nsted acid is p -toluene sulfonic acid, whether anhydrous form or as monohydrate.
- the co-catalyst is selected from phenolic compounds with one or more substituents, and quinone compounds.
- the co-catalyst is selected from phenol, hydroquinone, p- methoxyphenol, p -trifluoromethyl phenol, 1,4-benzoquinone, 1,4-naphthoquinone, and mixtures thereof. More preferably the co-catalyst is hydroquinone.
- the catalyst and co-catalysts present are also polymerisation stabilisers.
- the combined use of a Bronsted acid catalyst with hydroquinone as a co-catalyst has not been previously described for the direct synthesis of electron deficient olefin monomers such as cyanoacrylates.
- the preferred Br ⁇ nsted acid catalyst and co-catalyst concentrations are comprised between 2 mol% and 5 mol% of Br ⁇ nsted acid and between 0.02 mol% and 8 mol% of co-catalyst, relative to active methylene compound of general formula (III).
- the conditions applied in the three-component embodiment also apply to the two-component embodiment.
- the preferred ratio of active methylene compound to acylal is 1:1.
- the two-component embodiment may also optionally deploy additional stabilisers as described for the three-component embodiment.
- the process of the present invention has advantages over the prior art indirect and direct methods aside from circumvention of the aggressive cracking needed by the former.
- inventive catalyst system also comprises compounds known to function as free radical stabilisers that are co-catalysts. Acids inhibit polymerisation which is especially desirable in methods wherein monomer is unprotected in reaction milieux and in subsequent process steps. Avoidance of the use of N-based catalysts is desirable since inadvertent release of basic compounds from ammonium or iminium salts under process conditions presents a risk, even in the presence of excesses of protonic acids. Even trace levels of basic compounds are potent initiators for the polymerisation of such monomers.
- the process of the invention is applicable to industry for the facile one-pot preparation of reactive monomers for use in adhesives, sealants and coatings.
- the methods described deploy low loadings of simple commercially available catalysts and co-catalysts that also assist stabilisation of the reaction even under concentrated conditions.
- Standard methods are known that convert carboxylic acids to their anhydrides, and the latter have been shown to be promoters for the monomer forming reaction itself or are known reactants that in turn can be used to pre-form acylals that can be used in the monomer forming reaction.
- Electron deficient monomers are isolated by fractional distillation preferably employing vapour trail stabilisation using volatile free radical and Lewis acids stabilisers and collecting monomer onto stabilisers at previously indicated concentration levels. Volatile reaction components such as solvents and/or excess reagents if present, and by-products such as carboxylic acids are easily removed by evaporation and fractional distillations since their boiling points are much lower than target monomers. All evaporation or distillation equipment used for condensing vapour and collecting reactive monomer is usually passivated before use by pre-washing with, for example, 10% sulfuric acid, rinsing with distilled water and thoroughly dried before use.
- the process demonstrates isolation of pure highly reactive monomer by direct distillation from the reaction medium when starting materials are converted without the need for any intermediate processing steps. Circumventing the need to interrupt processing from synthesis to distillation lends the inventive methods to batch or continuous processing.
- the method is high yielding even for the most reactive ethyl cyanoacrylate monomer, with or without the use of additional solvents.
- the method does not produce large quantities of residue or waste, such as crack-residue or intractable masses of salts that must be disposed of.
- the reagents and catalyst were simply mixed together in one-pot and the reaction was conducted at temperature and for specific times.
- Lewis acids such as InCl 3 are deliquescent solids and were used as received.
- non-nucleophilic solvents such as toluene, p-xylene is optional.
- an electron deficient olefin may be prepared by reacting a cyanoacetate with a source of aldehyde in the presence of certain Lanthanide or transition metal Lewis acid catalysts.
- aldehyde compound is selected from the group paraformaldehyde, formalin, 1,3,5-trioxane, methylene diacetate, dimethoxymethane and acrolein. Some of these reactants, were tested in comparative experiments.
- the active methylene compound n -butyl cyanoacetate (BCAc) may be reacted with the acylal methylene diacetate (MDAc) or a source thereof using an ammonium or iminium salt catalyst ( N -based organocatalyst) with a reaction time of 2 hours and a temperature in the range 120-130°C.
- MDAc acylal methylene diacetate
- N -based organocatalyst ammonium or iminium salt catalyst
- That patent describes in situ preparation of MDAc from paraformaldehyde and acetic anhydride with excess p -TsOH.H 2 O and in the presence of cyanoacetate which is a three-component approach therein described as the 'direct method' in Example 3 of said patent.
- MDAc was also pre-formed as a product from an independent reaction using sulfuric acid as catalyst (Example 1 of said patent) and reacted with n -butyl cyanoacetate in a two-component approach.
- MDAc was prepared in pure form by the method of Tomi ⁇ ka et al., op. cit., except using p -TsOH.H 2 O as catalyst.
- the pre-formed MDAc was reacted with a variety of different cyanoacetates in an equimolar stoichiometry using the N -based organocatalyst prepared as described in the US'145 patent (5 mol% piperazine, 15 mol% p -TsOH.H 2 O) for a 2-hour reaction time at 120°C. No hydroquinone was used in the reaction.
- the MDAc was formed by reacting 1,3,5-trioxane recrystalised from a 1:1 mixture of ethyl acetate-petroleum ether, with acetic anhydride and the excess p -TsOH.H 2 O.
- Ethyl cyanoacetate, 1,3,5-trioxane and acetic anhydride were employed using 1:1:2 molar equivalents respectively in a mixture.
- the mixture was heated to 120°C and maintained at this temperature for between 1.5 and 2 hours.
- the result for the conversion of ethyl cyanoacetate directly to the corresponding ethyl cyanoacrylate, i.e., selectivity to monomer only, measured by 1 H-NMR was only 15%.
- Example 1 shows that the selectivity obtained in Example 1 is much superior to the selectivity obtained from an N -based organocatalysed equivalent three-component reaction (Comparative Example 3e).
- the one-pot three-component reaction was simple and convenient to perform from readily available starting materials and acetic acid by-product was clearly present in the reaction mixture as evidenced by 1 H-NMR.
- Example 1e the selectivity and conversion were boosted even further to 75% and 90% respectively as measured by 1 H-NMR, when p -xylene was added to the reaction mixture as solvent.
- Co-catalysts for the three-component embodiment was examined using a catalyst system employing 1 mol% InCl 3 , 5 mol% p -TsOH.H 2 O and various co-catalysts at concentrations indicated in Table III that also includes the result of Examples 1a and 1e for convenience of comparison.
- the molar ratio of ethyl cyanoacetate to 1,3,5-trioxane to acetic anhydride was 1:1:2 and reaction time was 2 hours at 120°C.
- a mixture comprising 10 g ethyl cyanoacetate, 9 g 1,3,5-trioxane, and 20 g of acetic anhydride was stirred and heated to 120°C for 5 hours in the presence of the catalyst system comprising 1 mol% InCl 3 , 5 mol% hydroquinone and 5 mol% p -TsOH.H 2 O.
- a mixture comprising 1100 mg ethyl cyanoacetate, 1300 mg methylene diacetate was stirred and heated to 120°C for 1 hours in the presence of the catalyst system comprising 5 mol% hydroquinone and 5 mol% p -TsOH.H 2 O.
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Claims (15)
- Verfahren zur Herstellung von elektronenarmen Olefinmonomeren, dadurch gekennzeichnet, dass eine aktive Methylenverbindung der allgemeinen Formel (III),
EWG-CH2-Z1 (III)
in der die zwei durch EWG und Z1 dargestellten elektronenziehenden Gruppen aus Nitril-, Carbonsäureester- und Carbonsäure-Funktionsgruppen ausgewählt sind,
entweder mita) einer Mischung aus einer Formaldehydquelle und einem Carbonsäureanhydrid der allgemeinen Formel (IV),
in Gegenwart eines Katalysatorsystems, das Folgendes umfasst:i) mindestens eine Säure, oderii) mindestens eine Säure und mindestens einen Cokatalysator,wobei die Säure aus der Gruppe der Lewis- und Brønsted-Säuren ausgewählt ist und der mindestens eine Cokatalysator aus der Gruppe der Phenolverbindungen mit einem oder mehreren Substituenten und Chinonverbindungen ausgewählt ist, oderb) einem Methylendiester der allgemeinen Formel (V),
in Gegenwart eines Katalysatorsystems, das eine Brønsted-Säure und mindestens einen Cokatalysator umfasst, ausgewählt aus der Gruppe der Phenolverbindungen mit einem oder mehreren Substituenten und Chinonverbindungen, umgesetzt wird. - Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die aktive Methylenverbindung der allgemeinen Formel (III),
EWG-CH2-Z1 (III)
in der die zwei durch EWG und Z1 dargestellten elektronenziehenden Gruppen aus Nitril-, Carbonsäureester- und Carbonsäure-Funktionsgruppen ausgewählt sind,mit einer Mischung aus einer Formaldehydquelle und einem Carbonsäureanhydrid der allgemeinen Formel (IV),in Gegenwart eines Katalysatorsystems, das Folgendes umfasst:i) mindestens eine Säure, oderii) mindestens eine Säure und mindestens einen Cokatalysator,wobei die Säure aus der Gruppe der Lewis- und Brønsted-Säuren ausgewählt ist und der mindestens eine Cokatalysator aus der Gruppe der Phenolverbindungen mit einem oder mehreren Substituenten und Chinonverbindungen ausgewählt ist, umgesetzt wird. - Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die aktive Methylenverbindung der Formel (III) ein Nitril und einen Carbonsäureester als elektronenziehende Funktionsgruppen umfasst.
- Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Formaldehydquelle aus trockenem Formaldehydgas, Paraformaldehyd und 1 ,3,5-Trioxan, bevorzugt 1 ,3,5-Trioxan, ausgewählt ist.
- Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Katalysatorsystem aus einer Lewis-Säure, bevorzugt einer Post-Übergangsmetall-Lewis-Säure, einer Kombination aus einer Lewis-Säure, bevorzugt einer Post-Übergangsmetall-Lewis-Säure, und einer Brønsted-Säure; einer Kombination aus einer Lewis-Säure, bevorzugt einer Post-Übergangsmetall-Lewis-Säure, und einem Cokatalysator, ausgewählt aus Phenolverbindungen mit einem oder mehreren Substituenten, Chinonverbindungen und Mischungen davon; einer Kombination aus einer Brønsted-Säure und einem Cokatalysator, ausgewählt aus Phenolverbindungen mit einem oder mehreren Substituenten, Chinonverbindungen und Mischungen davon, und einer Kombination aus einer Lewis-Säure, bevorzugt einer Post-Übergangsmetall-Lewis-Säure, und einer Brønsted-Säure und einen Cokatalysator, ausgewählt aus Phenolverbindungen mit einem oder mehreren Substituenten, Chinonverbindungen und Mischungen davon, ausgewählt ist, wobei eine Kombination aus Lewis-Säure, bevorzugt einer Post-Übergangsmetall-Lewis-Säure, einer Brønsted-Säure und einem ausgewählten Cokatalysator aus phenolischen Verbindungen mit einem oder mehreren Substituenten, Chinonverbindungen und Mischungen davon, bevorzugt wird.
- Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Cokatalysator aus Phenol, Hydrochinon, p-Methoxyphenol, p-Trifluormethylphenol, 1,4-Benzochinon, 1,4-Naphthochinon und Mischungen davon ausgewählt ist, wobei Hydrochinon bevorzugt wird.
- Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Lewis-Säure aus Übergangsmetallhalogeniden, Halogeniden auf Post-Übergangsmetallbasis, bevorzugt Trihalogeniden, Perchloraten auf Erdalkalimetallbasis und Lanthanidmetallbasis ausgewählt ist, bevorzugt ausgewählt aus der Gruppe der Post-Übergangsmetalle, besonders bevorzugt aus Indium(III)-Trihalogenid und Gallium(III)-Trihalogenid, bevorzugt Trichloride, und noch bevorzugter die Lewis-Säure InCl3 ist.
- Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Brønsted-Säure aus p-Toluolsulfonsäure, Benzolsulfonsäure und Aralkylsulfonsäuren ausgewählt ist, wobei p-Toluolsulfonsäure, entweder in wasserfreier Form oder als Monohydrat, bevorzugt wird.
- Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass es die Verwendung von Stabilisatoren, ausgewählt aus Säurestabilisatoren, bevorzugt ausgewählt aus Bortrifluoridetherat, SO2, Trifluoressigsäure, besonders bevorzugt Bortrifluoridetherat; und Radikalstabilisatoren, bevorzugt ausgewählt aus 2,2'-Methylenbis-(6-tert-Butyl-p-Kresol), Pentaerythritol-Tetrakis[3-[3,5-di-tert-Butyl-4-Hydroxyphenyl]propionathydrochinon, 4-Methoxyphenol, butyliertes Hydroxyanisol und butyliertes Hydroxytoluol, umfasst.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die aktive Methylenverbindung der allgemeinen Formel (III),
EWG-CH2-Z1 (III)
in der die zwei durch EWG und Z1 dargestellten elektronenziehenden Gruppen aus Nitril-, Carbonsäureester- und Carbonsäure-Funktionsgruppen ausgewählt sind,mit einem Methylendiester der allgemeinen Formel (V),in Gegenwart eines Katalysatorsystems, das eine Brønsted-Säure und mindestens einen Cokatalysator umfasst, ausgewählt aus der Gruppe der Phenolverbindungen mit einem oder mehreren Substituenten und Chinonverbindungen, umgesetzt wird. - Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass eine aktive Methylenverbindung der allgemeinen Formel (III) wie in einem der Ansprüche 3 bis 5 definiert verwendet wird.
- Verfahren nach Anspruch 10 oder 11, dadurch gekennzeichnet, dass der Methylendiester Methylendiacetat ist.
- Verfahren nach einem der Ansprüche 10 bis 12, dadurch gekennzeichnet, dass eine Brønsted-Säure wie in Anspruch 8 definiert verwendet wird.
- Verfahren nach einem der Ansprüche 10 bis 13, dadurch gekennzeichnet, dass ein Cokatalysator wie in Anspruch 6 definiert verwendet wird.
- Verfahren nach einem der Ansprüche 10 bis 14, dadurch gekennzeichnet, dass es Stabilisatoren wie in Anspruch 9 definiert umfasst.
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TW112112034A TW202346259A (zh) | 2022-07-11 | 2023-03-29 | 製備缺電子烯烴單體的方法 |
PCT/EP2023/058198 WO2023131729A1 (en) | 2022-07-11 | 2023-03-29 | Process for preparing electron-deficient olefin monomers |
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JPH0491069A (ja) | 1990-08-07 | 1992-03-24 | Three Bond Co Ltd | 新規なα―シアノアクリレートおよび接着剤組成物 |
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PT103272A (pt) * | 2005-05-06 | 2006-11-30 | Univ Do Minho | Processo para a preparação de alfa-cianoacrilatos de alquilo e alcoxialquilo por despolimerização de poli(alfa-cianoacrilatos de alquilo ou alcoxialquilo |
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GB2558264B (en) | 2016-12-23 | 2019-11-20 | Henkel IP & Holding GmbH | Process for preparing electron deficient olefins |
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